Photographic fixer-developer containing compounds with p-aminophenol and dyeforming nuclei

ABSTRACT

Photographic fixer-developer for silver halide layers, characterized in that it contains an alkaline compound, a fixing agent, e.g., sodium, potassium or ammonium thiosulfate, and at least one developer-coupler compound having within the same molecule a p-aminophenol nucleus capable of developing a silver halide image and a separate dye-forming nucleus capable of forming a quinoneimine or azomethine dye. The p-aminophenol nucleus is linked to the dye nucleus through a GROUP, FREE BONDS ATTACHED TO C and to N are attached to cyclic carbons. The fixer-developers are superior to prior developers with regard to contrast and maximum image density.

United States Patent Dieter Klein Gotzenhain;

Gerhard Heirnann, Neu-lsenburg; Werner, Abele Neu-lsenburg; Gerd. Joh. Oosterloo, Neu-Isenburg, all of Germany 10,616

Feb. 11, 1970 Oct. 26, 1971 E. l. du Pont de Nemours and Company Wilmington, Del.

[72] Inventors [2 l Appl. No. [22] Filed [451' Patented [7 3] Assignee [54] PHOTOGRAPHIC FIXER-DEVELOPER CONTAINING COMPOUNDS WITH p- AMINOPHENOL AND DYE-FORMING NUCLEI 6 Claims, N0 Drawings v [52] US. Cl 96/61 M, 96/66, 96/55 [51] lnt.Cl G03c 5/38, G03c 5/30, G03c 7/00 [50] Field of Search 96/55, 66,

29,61,61 M,66 l-lD [56] References Cited Primary Examiner-Norman G. Torchin Assistant Examiner-Mary F. Kelley Attorney-Lynn Barratt Morris ABSTRACT: Photographic fixer-developer for silver halide t layers, characterized in that it contains an alkaline compound,

a fixing agent, e.g., sodium, potassium or ammonium thiosulfate, and at least one developer-coupler compound having within the same molecule a p-aminophenol nucleus capable of developing a silver halide image and a separate dye-forming nucleus capable of forming a quinoneimine or azomethine dye. The p-aminophenol nucleus is linked to the dye nucleus through a -CH2N group, free bonds attached to C and to N are attached to cyclic carbons. The fixer-developers are superior to prior developers with regard to contrast and maximum image densiroan/nae NUCLEH The object of the present invention is a photographic fixerdeveloper (monobath) for the simultaneous developing and fixing of silver halide emulsions.

Developing and fixing photographic silver halide emulsions in practice are generally carried out in separate baths. However, there also exists the possibility of combining the two operations in one bath, the so-called monobaths. Such monobaths permit simplification and substantial shortening of the total operation, so that particularly in recent times, when ever shorter processing times are sought, they have gained increased importance. That, so far, monobaths have not been introduced to a great extent in practice is due chiefly to the fact that on using the monobath, as a rule, one must accept a loss in density and sensitivity compared with the conventional twobath system.

In fixing-developing, the developing and fixing processes proceed simultaneously, that is, the fixing process starts with the beginning of the development. Accordingly, a part of the exposed silver halide is dissolved already before the chemical development can take place. lndeed, through a physical developing process a part of the dissolved silver is reduced again and deposited on the silver image. However, because of its form, this silver has a very low covering power which, of necessity, leads to the situation that the sensitivity is inferior to that of conventional two-bath processing in all cases.

In the literature, fixer-developers are known that are supposed to operate with no or only a very small loss in sensitivity compared with the two-bath processing. It is common to all of these baths that they contain l-phenyl-3-pyrazolidone or amino-pyrazoline in superadditive mixture with a customary developer, usually hydroquinone. Such fixer-developers are described, for example, in the French Pat. No. 1,204,273; the German Pat. No. 1,024,798; the German Auslegeschrift No. 1,149,247 and the German Pat. No. 1,151,175.

However, through simultaneous developing and fixing and the incomplete utilization of silver halide connected therewith, the maximum developable density and also the gradation will be lower than in the conventional two-bath process. To compensate for this disadvantage in practice, it is customary to provide light-sensitive materials, that are destined for fixing-developing, with an increased silver halide coating weight.

Now, the problem of the invention is to create a photographic fixer-developer for silver halide emulsion films, that is superior to previously known one-bath systems in performance with respect to sensitivity utilization, contrast and maximum density. In doing this, not only should the otherwise unavoidable loss in density, gradation and practical sensitivity be compensated for in this process, but beyond this, compared with conventional development with separate fixing, an increase in sensitivity and density performance should be achieved without the necessity of an increased silver halide coating weight.

According to the invention, this problem is solved by using a fixer-developer which, in alkaline solution contains a fixing agent and at least one developer-coupler-compound with the following general fonnula:

on I

H s-z H,). R1 (am,

3 NH: 1 Xu in which a, b and n represent the numbers 0 or 1, m corresponds to I when n==0 and 2 when n=1 X is a negatively charged ion or an acid radical, for example, C l,

Z corresponds to R Rs in which at least one of the 2- and 4-positions is a free coupling position, for example, a hydrogen atom, halogen, -SO,H or an azo group or R and Z together represent the atoms necessary to form a 5- or 6-membered, nitrogen-containing, heterocyclic ring which can be substituted by Y, alkyl or a fused aromatic ring, wherein O H I" I Y stands for OH, N(Rt)z, N-CHQ or NH,

R corresponds to H, an alkyl radical with 1 to 4 carbon atoms, an aralkyl radical, a carboxymethyl radical, or unsubstituted and substituted aryl groups including --R and R1 R1 Y RI when n=l or is equal to R,, when 0,

R is equal to an alkyl radical with one to four carbon atoms,

R is equal to R Y corresponds to the previously given value of formula (I).

These developer-coupler compounds, as well as processes for their preparation, are described in Assignees Lugosy US. application Ser. No. 738,109, filed June 19, 1968.

The substances described are characterized in that, in addition to the silver image, they also build up a dye image, a property which makes them especially valuable for use in' monobaths.

The gain in density, through the formation of this additional dye image, is far greater than the loss in density and sensitivity observed in the optimum fixing-developing in the absence of self-coupling developing compounds, so that using the present process even light-sensitive materials with decreased silver ha lide coatings can be processed in the one-bath process with very good sensitometric results. The advantages of this finding for the production of special silver halide materials provided for one-bath processing are obvious: The production costs can be reduced, the image performance can be improved by reducing the film thicknesses, and the silver sludge deposition in the baths is reduced advantageously by reducing the quantity of silver salts dissolved out.

That the compounds described could be used with such good results for fixing-developing was surprising because these compounds, that are derived from p-aminophenoLpossess only a low developing speed compared with hydroquinone, for example.

On the other hand, however, it is known that for fixingdeveloping only developers are usable that are characterized by a rapid start and a high developing speed, because, only if the developing process starts after a time at which the exposed silver halide grains are still not dissolved to an appreciable extent by the presence of the fixing agent, can adequate densities be obtained. That, in the present case, in spite of the compara tively low developing speed, such a rapid and superior density buildup would result, could not be expected.

Depending on the nature of the developer-coupler compound, brown-black to black and/or colored images can be obtained.

Fixer-developers, that contain developer-coupler-compounds corresponding to the following formula preferentially deposit brown to blue-black dye images on the silver image:

UH -NR NH; Y

wherein R is H, alkyl of one to four carbons, aralkyl, or carboxymethyl, R, is equal to H, an alkyl radical with one to four carbon atoms, Cl, Br or -COOH, Y is equal to -OH or -NH,, whereby at least one of the 2 and 4 positions, capable of coupling, is unsubstituted. Also, compounds in which the nitrogen in the connecting radical -CH;N

represents a portion of a heterocyclic fiveor six-membered ring consisting of carbon and nitrogen atoms, are suitable developer-coupler'compounds which yield yellow or orangecolored images.

The developer-coupler compounds can be used alone or also in mixtures with one another. The use of a mixture is always recommended when special requirements are set regarding the color shade of the finished image.

The compounds are added to the one-bath solution suitably as salts, e.g., HCl or 11,80 salts, in amounts about 2 to 50 g./liter, preferably to 20 g./liter. Depending on the nature of the silver halide emulsion used, for example, as a function of the silver halide coating weight and other factors, the desired effect can be achieved perhaps with even smaller quantities or, when necessary, also with larger quantities without any adverse effect. The solutions, depending upon solubilities, may contain 10 to 150 g. or more per liter of the fixing agent, preferably Na, K or ammonium thiosulfate.

The monobath solutions of the invention, in addition to the essential constituents, may contain at least one developer-coupler compound with formula i, an alkali and fixing agent, all of the additives customary in developer solutions as well as antioxidants, development accelerators, stabilizers and the like.

In many cases, through an after treatment with an alkaline solution, that is carried out at the end of the washing process, the density of the image produced is increased and the color shade is influenced favorably. 7

Especially favorable results can be achieved with monobaths that contain the compounds of the invention in combination with one of the known black-and-white developers with superadditive action, e.g., N-methyl-P- aminophenol or any of the 3-pyrazolidones of Kendall, U.S. Pat. No. 2,289,367.

The photographic films processed with monobaths of the invention are characterized by sensitivity and density values that are so superior to those obtained in the two-bath process with separate developing and fixing, that it is possible to process light-sensitive materials with reduced silver halide coating weight in a one-bath process with very good results.

Moreover, the image-forming performance can be improved through reduction of the film thickness and the silver sludge deposition in the baths can be reduced favorably by reduction of the quantity of silver dissolved out.

The invention will be illustrated, but not limited, by the following examples. Obviously, the composition of the baths of the invention must be adjusted to the type of emulsion used at the time, which can be done in an optimum manner easily by any expert in the field.

EXAMPLE 1 Three strips of a panchromatically sensitized document film with a gelatin-silver halide emulsion with 70% AgCl and 30% AgBr, a gelatin-silver nitrate ratio of 0.6 and a coating weight corresponding to 47 mg. of AgNO per dm., were exposed for 0.02 sec. in a DIN (German Engineering Standard) apparatus (Osram tungsten lamp Wi 40/1, 2600 K.) with a continuous wedge (wedge constant 0.25/cm., light intensity at the wedge lux), and processed according to A, B and C.

A 15 g. sulfate of N-(2'-hydroxy-5'- aminobenzyl-3-hydroxyaniline 0.3 g. l-phenyl-3-pyrazolidone g. NaBO,.4H,O

50 g. Na,SO, anhydrous s g. KOH

40 g. Na,s,o,.sH,0

3 g. KBr

l g. disodium salt of ethylene diaminetetra-acetic acid 8 ml. ethylene glycol up to l l. with water pH=l L4 In this solution, strip 1 was fixed-developed at 20 C. for 3 min. Subsequently, it was washed for 3 min., aftertreated in a final bath containing 0.15 g. of ascorbic acid, 0.4 g. of NaOH and 5 g. of Na,CO per liter of water and dried. B Strip 2 was processed in a fixer-developer analogous to A with 15 g. of hydroquinone instead of N-(2'-hydroxy-5 aminobenzyl)-3-hydroxyaniline for 3 min. at 20 C., washed with water for 3 min. and dried. C Strip 3 was developed under the same conditions in a conventional developer having the following composition, fixed after washing and dried:

15 g. hydroquinone 0.3 g. l-phenyl-3pyrazolidone 50 g. Na,C0, anhydrous 60 g. Na,SO, anhydrous 0.3 g. K,S,0, 2 g. disodium hexametaphosphatc 1.1 g. disodium salt of ethylene diaminetetra-acetic acid 0.2 g. KNO, 3 g. KBr 0.1 g. benztriazole Four strips of an X-ray film coated on both sides with a gelatin-silver halide emulsion with 98.3% AgBr and 1.7% Agl, a gelatin-silver nitrate ratio of 1.0 and a cast coating corresponding to 60 mg. of AgNo per din. were exposed for 2 sec. in an exposure apparatus (2 Osram lamps Wi 9, 2600 K, two blue Jena filters, type B63 (1.9 mm.) and BG 38 (1.5 mm.), with a light intensity on the gray continuous wedge of 20 lux (wedge constant 0.] 5/cm.), and processed according to A, B, C and D.

A 20 g. sulfate of N-(Z'hydroxy-S aminobenzyl)-3-hydroxyuniline 0.5 g. l-phenyl-J-pyrazolidone 150 g. mao,.4u,o 50 g. "-80, anhydrous l4 KOl-l 40 g. m,s,o,.sn,o l g. disodium salt of ethylenediamine dried.

tetraacetic acid g. KBr g. thiosalicylic acid l l. with water up to pH=l 2.3

Strip 1 was fixed-developed for 3 min. at C. in the 5 developer described under A, washed, after-treated and dried according to the procedure in example 1.

B Strip 2 was fixed-developed for 3 min. at 20 C. in the developer described under A which contained in addition 0.5

g. of l-phenyl-3 pyrazolidone and was washed, after treated and dried according to the procedure in example 1.

C Analogous to example 28, strip 3 was fixed-developed for 3 min. at 20 C. with 20 g. of hydroquinone instead of N-(2'- hydroxy-S'-aminobenzyl)-3-hydroxyaniline, washed and D Strip 4 was processed at 20 C. for 3 min. in the developer described under example 1C with subsequent fixing.

Relative Maximum Gradation example 1 Referred to Strip Relative Maximum Gradation 4, Example 2 sensitivity density l .6 2.7 2.6 EXAMPLE 4 An exposed strip of X-ray film was processed in the following fixer-developer for 3 min. at 20 C:

20 g. sulfate of N-methyl-N(2'-hydroxy-5 aminobenzyl)-3aminoaniline 0.5 g. Lphcnyl-Ii-pyrazolidone I50 g. NaBO,.4H,O

40 g. Na,S,O,,5H,O 14 g. KO"

1 g. ethylenediamenetetraacetic acid disodium salt 3 g. KBr 0.1 G. thiosalicylic acid up to l l. with water pH=l 2.9

Subsequently, it was washed, after-treated and dried as in example 1A.

Referred to Strip Relative Maximum Gradation 3, Example 2 sensitivity density EXAMPLE 5 An exposed strip of X-ray film was processed in the following fixer-developer for 3 min. at 20 C.:

20 g. sulfate of N-(2'-hydrnxy -5 '-aminobenzyl)- 3-aminn-6-carhoxyaniline 0.5 g. l-phenyl-3-pyrazolid0ne g. NaB0,.4H,O

60 g. Na,s,0,.s11,o 14 g. KOH

l g. disodium salt of ethylenediamine tetra-acetic acid 5 g. KBr

up to l l. with water pH=l2.4

Subsequently, it was washed, after-treated and dried as in example lA.

Referred to strip Relative Maximum Gradation 3, Example 2 sensitivity density EXAMPLE 6 An exposed strip of X-ray film was processed in the following fixer-developer for 3 min. at 20 C 10 g. sulfate uf N-(T'hydrmty-S' -aminobenzyl)-3-hydroxyaniline IO g. sulfate of N-(2'-hydroxy-5' aminobenzyl)-3-aminoaniline 14 3. X011 150 g. NaBO,.4H,O 50 g. Na,SO, anhydrous 40 g. Na,s,o,.s1i,o

5 g, KBr 0.5 g. l-phenyl-B-pyrazolidone l g. disodium salt of ethylenediaminetetraacetic acid up to l l. with water H=l2.5

Relative Maximum Gradation sensitivity density Suitable alkaline compounds that may be present in the fixer-developers of this invention include sodium and potassium hydroxide, sodium acetate, sodium and potassium carbonate, trisodium phosphate, borax and amines, e.g.,

, triethanolamine, in an amount to give the desired pH, usually 8-! 3. As indicated in the examples, sodium metaborate also is useful in such an amount.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

I. Photographic fixer-developer for the simultaneous developing and fixing of photographic silver halide emulsions, characterized by containing an alkaline compound, a fixing agent and at least one developer-coupler compound with the following general formula:

in which a, b and n represent the numbers 0 or 1, m corresponds to 1 when n=0 and 2 when n=l X is a negatively charged ion or an acid radical, for example, C l

Z corresponds to R in which at least one of the 2- and 4-positions is a free coupling position, for example, a hydrogen atom, halogen,

S0, or an azo group or R and Z together can indicate the atoms necessary to form a or 6-membered, nitrogen-containing, heterocyclic ring which can be substituted by Y, alkyl or a fused aromatic ring, whereby H I Y stands for 0H, N(R4)2, N-CH,

R c'site gaKfiJ radical with one to four carbon atoms, an aralkyl radical, a carboxymethyl radical, or unsubstituted and substituted aryl groups including R1 g R3 and R1 R1 R1 Y El in which R is equal to H, an alkyl radical with one to four carbon atoms, Cl, Br or -COOH,

R is equal to H, an alkyl radical with one to four carbon atoms, Cl or Br, OH or NH R represents a linkage to when n=l, or is equal to R W R is equal to an alkyl radical with one to four carbon atoms,

R, is equal to R,,

Y corresponds to the previously given value in Formula (I),

2. An aqueous developer-fixer according to claim 1 containing per liter of solution 2 to 50 grams of the developer-coupler compound and to 150 grams of sodium, potassium or ammonium thiosulfate.

3. Photographic fixer-developer according to claim 1, characterized in that it contains a developer-coupler com pound with the following general formula:

5. Photographic fixer-developer according to claim 1, characterized in that it contains a developer-coupler compound with the following general formula:

| I CH:NH

| NE: NH:

6. Photographic fixer-developer according to claim 1, characterized in that, in addition to at least one developercoupler compound, it contains N-methyl-p-aminophenol or a 3-pyrazolidone developing agent. 

2. An aqueous developer-fixer according to claim 1 containing per liter of solution 2 to 50 grams of the developer-coupler compound and 10 to 150 grams of sodium, potassium or ammonium thiosulfate.
 3. Photographic fixer-developer according to claim 1, characterized in that it contains a developer-coupler compound with the following general formula:
 4. Photographic fixer-developer according to claim 1, characterized in that it contains a developer-coupler compound with the following general formula:
 5. Photographic fixer-developer according to claim 1, characterized in that it contains a developer-coupler compound with the following general formula:
 6. Photographic fixer-developer according to claim 1, characterized in that, in addition to at least one developer-coupler compound, it contains N-methyl-p-aminophenol or a 3-pyrazolidone developing agent. 